JP3451804B2 - Polycarbonate resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] [0001] The present invention relates to a polycarbonate.
Compatibility with olefin-based resins improves heat resistance and
Excellent balance of mechanical strength such as tensile strength and weld strength
Polycarbonate with excellent moldability that gives molded products with excellent appearance
And a carbonate-based resin composition. This resin molded product
Is a wheel cap, instrument panel, door
Automotive parts such as trim and housing for electric and electronic equipment
It can be used for ring, knob, dial, etc. [0002] 2. Description of the Related Art Polycarbonate is impact resistant and dimensionally stable
Has excellent properties such as heat resistance and optical transparency.
Used for various applications such as hollow containers and toys
You. However, the melt fluidity is poor, making molding difficult.
And has poor water absorption resistance and organic solvent resistance.
You. On the other hand, propylene resin and ethylene resin
Olefins represented by fats and oils have good moldability,
Excellent in water resistance and organic solvent resistance, low specific gravity and inexpensive.
Used for film, hollow containers, toys, etc.
ing. A single resin material fully satisfies the desired properties.
If not, mix with other resin materials
As a result, techniques that complement inadequate properties are
You. With this, polycarbonate and olefin resin
Resin composition that has both good properties of
If a product is obtained, the field of use can be expanded. However, polycarbonate having a polar group
And hydrophobic olefin resins are inherently incompatible
And no affinity, so simply mixing both components
The adhesiveness of the interface of this two-phase structure is not good. That
As a result, the phase interface of the resulting molded product becomes defective,
And other mechanical strength. The two phases are uniform and
Difficult to form a fine dispersion form, when molding such as injection molding
Delamination (delamination)
) Is likely to occur and molded products with poor appearance are likely to be produced. [0005] In order to solve the above problems, poor reactivity is required.
Reacts with new olefin resin with polycarbonate
Modified olefin resin with a functional group introduced into polycarbonate
It has been proposed to be incorporated into a sheet. For example, Olef
Styrene monomer and maleic anhydride
Formed by co-grafting unsaturated carboxylic acid derivatives such as
Resin composition of modified olefin resin and polycarbonate
The product is disclosed in Japanese Patent Application Laid-Open No. 3-285937.
However, molded products obtained from these resin compositions are dispersed
Insufficient properties, easy to delaminate, practical appearance and impact resistance
Not satisfactory. Also, an aromatic vinyl monomer and glycidyl meta
Melt the polar functional group-containing vinyl monomer such as acrylate
Modified propylene resin reacted with different propylene resins
The dispersibility and impact of the resulting molded article
The improvement in strength and the like is disclosed in JP-A-5-295221.
Although it is disclosed in the gazette, further improvement is required.
You. On the other hand, hydroxyethyl methacrylate and the like
Modified with hydroxy group-containing (meth) acrylate
Resin composition of ren or polypropylene and polycarbonate
Products are disclosed in JP-A-3-39342 and JP-A-3-39344.
Nos. 3 and 4 are disclosed in each gazette. However, this resin set
The product is a hydroxyl group-containing (meth) acrylate-modified olefin.
Heat-kneading strips with insufficient heat stability
Under these conditions, hydroxyl groups that effectively react with polycarbonate disappear.
The problem is that
The physical properties of the shapes are not practically satisfactory. [0008] SUMMARY OF THE INVENTION The present invention provides a stable dispersion
Gives molded products with a structure and excellent mechanical strength and appearance
It is an object of the present invention to provide a thermoplastic resin composition. [0009] Means for Solving the Problems The present invention relates to a method for preparing the component (A).
Polycarbonate having a weight average molecular weight of 10,000 to 150,000
-Carbonate 10 to 99% by weight and component (B) olefin
100 parts by weight of a resin composition comprising 90 to 1% by weight of a resin
On the other hand, component (C) a hydroxyl group-containing α, β-unsaturated carboxylic acid
Heat-modified with modified olefin resin grafted with acid ester
Polyester obtained by subjecting a plastic polyester to a reaction process
Steal-modified olefin resin is 1 to 100 parts by weight
The modified olefin resin is composed of
Hydroxyl-containing α, β-unsaturated in 100 parts by weight of fin-based resin
Carboxylic acid ester 0.01 to 20 parts by weight and aromatic bicarbonate
Graft polymerization step with 0.01 to 50 parts by weight of phenyl monomer
Is a modified olefin resin obtained by applying
It is intended to provide a carbonate-based resin composition. [0010] [Action] Component (A) polycarbonate and component (B) ole
Polycarbonate of the present invention in which fin-based resin is well compatible
The reason why the resin-based resin composition can be provided is as follows.
(C) A polyester-modified olefin resin is used as a compatibilizer.
It seems that it is functioning. Specifically, component (C)
Olefin part of polyester-modified olefin resin
Is compatible with the unmodified component (B) olefin resin,
(C) Polyester modified olefin resin
The ter moiety may be the same as the component (A) polycarbonate
Are considered to be compatible by transesterification
You. [0011] DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.
You.Component (A) polycarbonate The polycarbonate used in the present invention is an aromatic dihydroxy.
Compound or a small amount of the polyhydroxy compound,
It is produced by reacting with phosgene. Also,
Aromatic dihydroxy compound or a small amount of polyphenol
Transesterification of the droxy compound with carbonic acid diester
Even manufactured. If necessary, a trifunctional or higher functional compound of the branching agent
The product and the molecular weight modifier are also provided for the reaction. Polycarbonate of the present invention
Bonate is a thermoplastic aromatic polycarbonate with or without branching.
It is a carbonate. Examples of the aromatic dihydroxy compound include:
2,2-bis (4-hydroxyphenyl) propane (hereinafter referred to as
Abbreviated as bisphenol A), tetramethylbisph
Enol A, tetrabromobisphenol A, bis (4
-Hydroxyphenyl) -p-isopropylbenzene,
Hydroquinone, resorcinol, 4,4'-dihydro
Xiphenyl, bis (4-hydroxyphenyl) meta
, Bis (4-hydroxyphenyl) ether, bis
(4-hydroxyphenyl) sulfone, bis (4-hydrido)
Roxyphenyl) sulfoxide, bis (4-hydroxy
Phenyl) sulfide, bis (4-hydroxyphenyl)
Le) ketone, 1,1-bis (4-hydroxyphenyl)
Ethane, 1,1-bis (4-hydroxyphenyl) cyclo
Bisphenol A, especially bisphenol A
No. [0013] The branched polycarbonate is a
Logurcine, 4,6-dimethyl-2,4,6-tri (4
-Hydroxyphenyl) heptene-2,4,6-dimethyl
Ru-2,4,6-tri (4-hydroxyphenyl) hep
Tan, 2,6-dimethyl-2,4,6-tri (4-hydr
Roxyphenyl) heptene-3,2,6-dimethyl-
2,4,6-tri (4-hydroxyphenyl) hepta
1,3,5-tri (4-hydroxyphenyl) ben
Zen, 1,1,1-tri (4-hydroxyphenyl) d
Polyhydroxy compounds exemplified by tan and the like, and 3,
3-bis (4-hydroxyaryl) oxindole
[= Isatin (bisphenol A)], 5-chloroisa
Tin, 5,7-dichloroisatin, 5-bromoisatin
Etc., a part of the dihydroxy compound, for example, 0.1
~ 2 mol% can be obtained by substitution. Furthermore, a monovalent compound suitable for controlling the molecular weight
As the aromatic hydroxy compound, m- or p-
Tylphenol, m- or p-propylphenol
, P-bromophenol, p-tert-butylpheno
And p-long chain alkyl-substituted phenols, and the like.
It is. Suitable polycarbonates include bis (4-h
(Droxyphenyl) alkane compounds, particularly preferably
A polycarbonate made mainly of bisphenol A
You. Obtained by using two or more aromatic dihydroxy compounds in combination
Polycarbonate copolymer, trivalent phenol
Branched polycarbonate obtained by using small amounts of compounds
Can also be mentioned as a preferred example (JP-A-63-30).
No. 524, No. 56-55328, Japanese Patent Publication No. 55-414
No. 60-25049, Tokuho 3-49930
Gazette). In addition, polycarbonate is a mixture of two or more
You may use it. The molecular weight of the preferred polycarbonate is heat resistant.
GPC from the balance of properties, mechanical strength, moldability, etc.
Weight average molecular weight (M
w) ranges from 10,000 to 150,000, and 1
The range of 5,000 to 100,000 is more preferable, and
Most preferably, the range is from 5,000 to 80,000. [0016]Component (B) olefin resin The olefin resin used in the present invention has 2 to 10 carbon atoms.
X-ray diffraction comprising at least one α-olefin
Is preferably 15% or more at room temperature,
It is preferably 30 to 70% and has a melting point of 60 ° C or more.
Is what you do. Crystallinity loss is the modulus of the final composition
Less than 15% of the crystallinity
System resins are not preferred. In addition, this olefin resin
Needs a sufficient molecular weight as a molding resin at room temperature
It is. For example, when propylene is the main component, JI
Melt flow rate measured according to SK 6758
G is 0.01 to 500 g / 10 min, preferably 0.05
Molecular weight corresponding to １００100 g / 10 min.
Flexural modulus according to K 7203 is 500 kg / cm^TwoLess than
Above, preferably 5,000-28,000 kg / cm^Two
Is good. The above α, which is a component of the olefin resin,
-Examples of olefins include ethylene, propylene,
Ten-1, pentene-1, hexene-1, 3-methylbu
Ten-1,4-methylpentene-1,3,3-dimethyl
Pentene-1,3-methylhexene-1,4-methyl
Xen-1,4,4-dimethylhexene-1,5-methyl
Lehexene-1, allylcyclopentane, allylcyclo
Hexane, allylbenzene, 3-cyclohexylbutene
-1, vinylcyclopropane, vinylcyclohexane,
2-vinyl-bicyclo [2,2,1] heptane, hepte
And octene-1 and the like.
May be used alone or in combination of two or more.
It can also be used. Preferred examples of the above include ethylene,
Propylene, butene-1, pentene-1, hexene-
1,3-methylbutene-1, 4-methylpentene-1,
3-methylhexene-1 can be mentioned. Especially d
Tylene, propylene, butene-1,3-methylbutene-
1,4-methylpentene-1 is preferred. In addition, other
4-methyl-1,4-hexadiene, 5
-Methyl-1,4-hexadiene, 7-methyl-1,6
Non-conjugated dienes such as octadiene and 1,9-decadiene
May be used as a part of the polymerization component. [0019]Component (C) polyester modified olefin
resin (1) Modified olefin resin Obtain the polyester-modified olefin resin used in the present invention
Olefin resin used for
Α, β-unsaturated carboxylic acid ester containing hydroxyl group
Can be obtained by grafting Olef
Hydroxyl-containing α, β-unsaturation grafted to vinyl resin
Carboxylic acid ester type can react with polyester
If there is no particular limitation, polyester using a catalyst etc.
It is also possible to react with. Hydroxyl group-containing α, β-
The following are examples of the saturated carboxylic acid ester.
It is. However, the following (meth) acrylates are
And methacrylate. example
For example, 2-hydroxyethyl (meth) acrylate, 2-
Hydroxypropyl (meth) acrylate, 2,3-di
Hydroxypropyl (meth) acrylate, 2-hydro
Xymethyl-3-hydroxypropyl (meth) acryle
2,2-dihydroxymethyl-3-hydroxypropyl
Ropyl (meth) acrylate having 4 to 40 carbon atoms
Tylene glycol or propylene glycol (
TA) (Meth) acrylic ester such as acrylic ester
, Bis (2-hydroxyethyl) fumarate, bis
(2-hydroxypropyl) fumarate, bis (2,3
-Dihydroxypropyl) fumarate, bis (2-hydr)
Roxymethyl-3-hydroxypropyl) fumarate,
Ethylene glycol having 4 to 40 carbon atoms or
Fumaric acid ester such as fumarate ester of pyrene glycol
Ters, and similar maleic acid esters, etc.
You. In addition, fumaric acid and maleic acid ester are as described above.
The two carboxyl groups are both hydroxyalkyl
Not only those esterified with the
Sterilized ones can also be exemplified as similar monomers.
You. In addition, N-methylol (meth) acrylamide and the like
(Meth) acrylamides can also be used. Among them, 2-hydroxyethyl
(Meth) acrylate, 2-hydroxypropyl (meth)
(T) acrylate, ethylene glycol having 4 to 40 carbon atoms
(Meth) acrylic alcohol or propylene glycol
Luic esters are preferred. Above hydroxyl group-containing α, β-
Saturated carboxylic esters may be used alone or in combination of two or more.
Can be used. The above hydroxyl group-containing α, β-unsaturated
Carboxylic acid ester grafted to olefin resin
When using an aromatic vinyl monomer together,
Grafting reaction of α, β-unsaturated carboxylic acid ester containing group
It is possible as long as the response is not hindered. Aromatic vinyl monomer
Use together to control the molecular weight of the modified olefin resin
This is also a very effective means. Examples of the aromatic vinyl monomer include styrene
Len, α-methylstyrene, t-butylstyrene, α-
Methyl vinyl toluene, α-methoxystyrene, nitro
Styrene, cyanostyrene, hydroxymethylstyrene
, Methylstyrene, dimethylstyrene, trimethyls
Tylene, chlorostyrene, dichlorostyrene, bromos
Tylene, dibromostyrene, vinyl naphthalene, vinyl
Pyridine, vinylimidazole and the like can be mentioned. these
Among them, styrene, α-methylstyrene, methylstyrene
Len is preferred. These aromatic vinyl monomers are simply
German or two or more can be used in combination. Hydroxyl-containing α, β-unsaturated carboxylic acid
The amount of the terpolymer added at the time of graft polymerization is
0.01 to 20 parts by weight with respect to 00 parts by weight, preferably
It is in the range of 0.1 to 10 parts by weight. Also, these hydroxyls
Group containing α, β-unsaturated carboxylic acid ester
When using vinyl monomers together, the aromatic vinyl monomer group
The amount added during raft polymerization is 100 weight of olefin resin
Part to 0.01 part by weight, preferably 0.1 to 50 parts by weight
It is in the range of 20 parts by weight. Α, β-unsaturated
Addition amount of both rubonic acid ester and aromatic vinyl monomer
If the amount is too large, the molding processability may decrease due to gelation or the like,
The appearance of the molded product may deteriorate,
No. It is also preferred in the following reaction with polyester.
I don't. Hydroxyl-containing α, β-unsaturated carboxylic acid
The ratio of the added amount of the ter and the aromatic vinyl monomer may be any value.
Although it can be performed within the range, the olefin during the graft reaction
When suppressing the decrease in the molecular weight of the resin, aromatic vinyl
With a hydroxyl group-containing α, β-unsaturated carboxylic acid ester
It is preferable to use at least equimolar. Contains the above hydroxyl group
α, β-unsaturated carboxylic acid ester and optionally aromatic
Of aromatic vinyl monomer to olefin resin
The method depends on the state of the reaction system such as solution, suspension, melting, and solid phase.
It is not limited to. In addition, radicals are formed in the reaction system.
As long as they occur, their sources are also particularly limited
Not something. Radical initiation to generate radicals
Agents are commonly used, examples of which include t-butyl
Hydroperoxide, cumene hydroperoxide,
2,5-dimethylhexane-2,5-dihydroperoxy
Sid, benzoyl peroxide, dicumyl peroxy
, 1,3-bis (t-butylperoxyisopropyl
B) benzene, t-butylperoxybenzoate, di
Butyl peroxide, methyl ethyl ketone peroxy
Organic and inorganic peracids such as potassium, potassium and hydrogen peroxide
2,2'-azobisisobutyronitrile, 2,2'-azobisisobutyronitrile
2'-azobis [2-methyl-N- (2-hydroxy
Tyl) propionamide], azodi-t-butane, etc.
Using carbon radical generators such as azo compounds and dicumyl
be able to. These radical initiators are optional
And two or more kinds may be used in combination. The amount of the radical initiator to be used is
0 to 30 parts by weight, preferably 100 parts by weight of the resin, preferably
It is in the range of 0 to 10 parts by weight. Temperature during grafting reaction
Is usually from 30 to 350 ° C, preferably from 50 to 300 ° C.
And the reaction time is 50 hours or less, preferably 0.1 hour.
The range is from 1 minute to 24 hours. Also, during the grafting reaction
Add other compounds as long as they do not interfere with the grafting reaction.
It is also possible to add. For example, to reduce molecular weight
Antioxidant to improve the reaction efficiency during the melting reaction
And the addition of an organic solvent such as xylene. [0026](2) Thermoplastic polyester Various saturated polyesters as thermoplastic polyesters
Can be used. For example, Zical according to the usual method
Bonic acid or its lower alkyl ester, acid halide
Or by condensing an acid anhydride derivative with glycol
Thermoplastic polyester. In producing this thermoplastic polyester,
As specific examples of suitable aromatic or aliphatic dicarboxylic acids
Are oxalic, malonic, succinic, glutaric,
Pinic acid, suberic acid, azelaic acid, sebacic acid,
Phthalic acid, isophthalic acid, 4,4'-dicarboxydiph
Phenyl sulfone, 4-carboxyphenoxyacetic acid, 4-
Carboxyphenoxypropionic acid, 4-carboxyphen
Enoxybutyric acid, 4-carboxyphenoxyvaleric acid, 2,
6-naphthalenedicarboxylic acid or 2,7-naphthalene
Dicarboxylic acid, etc., or a mixture of these carboxylic acids
No. Specific examples of glycols include ethylene glycol.
Recall, 1,3-propylene glycol, 1,4-butane
2 carbon atoms such as tandiol and 1,6-hexanediol
~ 12 linear alkylene glycols, pyrocatechol,
Aromatic glycols such as resorcinol and hydroquinone,
Alicyclic glycols such as cyclohexane dimethanol,
Or alkyl-substituted derivatives of these compounds.
It is. Suitable thermoplastic polyesters include
Polyethylene terephthalate, polybutylene terephthalate
G, polyethylene naphthalate, poly (1,4-cyclo
Hexane dimethylene terephthalate). Ma
Eastman Kodak X7G, Hoechst Serani
Corporation's Vectra, Sumitomo Chemical Co., Ltd.'s Econole, etc.
Liquid crystalline polyester marketed under the trade name
No. These thermoplastic polyesters may be used alone or in combination.
These can be used in combination. [0030](3) Polyester modified olefin resin
Manufacturing method Component (C) polyester-modified olefin used in the present invention
The modified resin is composed of the modified olefin resin and the thermoplastic resin.
It is obtained by reacting a ester. At the time of reaction
Ratio of modified olefin resin and thermoplastic polyester
Is in the range of 10:90 to 90:10 by weight,
More preferably, it is in the range of 20:80 to 80:20. Thermoplastic
If the amount of the conductive polyester is too small, polycarbonate
And the effect of compatibility with water is insufficient. Modified Oleph
The reaction method between the vinyl resin and the thermoplastic polyester is
The method is not limited to the general method such as a solution method and a melting method.
You can use any method that works.
No. However, practically, melt kneading is preferred. As a method of melt kneading, thermoplastic resin is used.
For this purpose, kneading methods generally used can be applied.
For example, if necessary, add powdery or granular components
Henschel mixer, ribbon blender with additional ingredients
-, Uniformly mixed with a V-type blender, etc.
Or multi-screw kneading extruder, roll, Banbury mixer, etc.
Can be kneaded. In addition, kneading under reduced pressure
Removes unnecessary components and deteriorates polyester.
It is also possible to suppress. Attachments that can be added during melt kneading
Additional components include organic solvents such as trichlorobenzene,
Tetrakis (2-ethylhexoxy) titanium and dibutyl
Or a transesterification catalyst such as diphenyltin oxide
Is mentioned. Further, the polyester has a higher molecular weight (low molecular weight).
Acid) of divalent metals such as magnesium oxide
Compounds, bisoxazoline compounds, diepoxy compounds, etc.
Bifunctional monomers can also be added. Also, birds
Phenyl phosphite, bis (2,6-di-tert-
Butyl-4-methylphenyl) pentaerythritol di
Phosphites such as phosphites are also used for similar purposes.
However, these catalysts may be used as catalysts such as potassium carbonate
Use of a metal salt further improves the effect. Also, each component
The melt-kneading temperature is in the range of 100 to 400 ° C, preferably
Is in the range of 120-300 ° C. [0033]Mixing ratio of resin composition The polycarbonate resin composition of the present invention comprises the component (A)
And 100 parts by weight of the resin composition comprising component (B)
1 to 100 parts by weight, preferably 10 to 80 parts by weight of the component (C)
Parts by weight, more preferably 30 to 50 parts by weight
It is. The ratio of the component (A) to the component (B) depends on various physical properties.
Component (A) is 10 to 90% by weight from the balance, component
(B) is 90 to 10% by weight, preferably component (A) is 2%.
0 to 80% by weight, component (B) is 80 to 20% by weight,
Preferably 30 to 70% by weight of component (A),
(B) is 70 to 30% by weight. Component (C) is added
If the amount is too small, the compatibility between the component (A) and the component (B) is not sufficient.
If the amount is too large, it is not preferable.
Transesterification reaction between stel and polycarbonate proceeds
Too much, which reduces the characteristics of polycarbonate
Not preferred. [0034]Additional ingredients The polycarbonate resin composition of the present invention comprises the above components
Other resin components other than (A) to (C) are used for the effect of the present invention.
It can be contained within a range that does not impair. For example,
Polyamides such as Ron 6, nylon 6,6, etc., polyacetators
And ABS resin. In addition, the poly
Carbonate-based resin composition has antioxidant and improved weather resistance
0.5 to 3 weight of chemicals, nucleating agent, flame retardant, slip agent, etc.
%, A plasticizer, a fluidity improver, a release agent, etc.
%, 1 to 10% by weight of a colorant and a dispersant thereof,
Machine / inorganic filler, reinforcing agent, especially glass fiber, mica,
Luku, wollastonite, potassium titanate, calcium carbonate
Containing 5-40% by weight of aluminum, silica, etc.
Effective for improving heat resistance, heat resistance, dimensional accuracy, dimensional stability, etc.
You. Further, an impact modifier is used in an amount of 5 to 30.
% By weight. As impact modifiers, styrene
Len-butadiene copolymer rubber, styrene-isoprene
Copolymer rubber, or hydrogenated product thereof, ethylene-
Propylene copolymer rubber, ethylene-propylene-die
Copolymer rubbers, their α, β-unsaturated carboxylic acids
Modified hydrate, unsaturated glycidyl ester or unsaturated
Glycidyl ether modified, and unsaturated epoxidation
Copolymer of ethylene and unsaturated epoxide
Consists of compounds, ethylene and ethylenically unsaturated compounds
Copolymers and the like can be used. [0036]Method for producing resin composition The method for preparing the polycarbonate resin composition of the present invention is
Is not limited to polyester modified olefins
Each method similar to that described in the manufacturing method for resin is applied
It is considered possible. The kneading order of each component is particularly limited.
(1) Polycarbonate, olefin
Resin and polyester-modified olefin resin
If any, additional ingredients are kneaded all at once. (2) Polycarbonate
-Molten carbonate and olefin resin
Add remaining ester modified olefin resin and other components
Kneading method, (3) olefin resin and polyester resin
Melt and mix the water-soluble olefin resin.
And a method of adding and kneading the remaining components other than the above.
It also includes the production of polyester-modified olefin-based resins.
, Continuous melting and kneading,
It is also possible to produce a fat composition. For example thermoplastic
The latter stage of the melting reaction between polyester and modified olefin resin
From polycarbonate and olefinic resin
And kneading. Polycarbonate of the present invention
The molding method of the resin composition is not particularly limited.
There are no components commonly used for thermoplastic resins.
Forming methods: injection molding, blow molding, extrusion, thermoforming
Various molding methods such as shape and press molding can be applied. [0037] The present invention will be described in more detail with reference to the following examples.
The present invention is limited by these
is not. Hydroxyl group grafted on modified olefin resin
Α, β-unsaturated carboxylic acid ester and aromatic vinyl
The content of structural units based on monomer
After purifying the olefin resin by the following method (1),
It was determined using the method of (2). Also, polyester modified
Polyester graft olefin in olefin resin
The system resin was quantified by the following method (3). (1) Method for purifying modified olefin resin:
0.3 g of the modified olefin resin obtained in the
Dissolve in 0ml xylene and heat to 110 ° C
I let it. Pour this solution into 159 ml of methanol to produce
The substance was reprecipitated, and this was separated by filtration. This reprecipitation purification operation
After repeating the procedure, dry under reduced pressure
A fat was obtained. (2) Infrared spectroscopy (hereinafter referred to as “IR method”)
U): Pressed molding machine for the purified modified olefin resin
Into a film, and measure the infrared absorption spectrum.
Absorption originating from the carbonyl of this spectrum and previously created
From the calibration curve obtained, the hydroxyl group-containing α, β-unsaturated carboxylic acid
The content of constituent units based on the ester was determined. Likewise
And the calibration curve prepared in advance
From the content of structural units based on aromatic vinyl monomer
Quantified. (3) Polyester graft olefin type
Resin quantification: 1 kg of polyester-modified olefin resin
20 ml of trichlorobenzene was added to the mixture at 180 ° C. for 30 minutes.
The mixture was stirred for dissolution and swelling. Then add 40 ml of xylene
In addition, the temperature is lowered to 130 ° C while stirring.
Solution with the unreacted olefin resin dissolved
Unreacted polyester and polyester graft
A mixed solution of an olefin resin was obtained. Transfer this mixed solution
130 ° C., 10,000 rpm, 3
Centrifuge for 0 minutes to remove unreacted polyester and polyester.
Recovering the tergraft olefin resin as a precipitate,
It was washed by filtration and dried under reduced pressure. In addition, the mixture
Add 30 ml of safluoroisopropanol, and add 5 ml at room temperature.
Unreacted polyester was dissolved by stirring for hours. this
Use a 0.45μm Teflon filter for the insoluble content of the solution
And filtered under reduced pressure, and then dried under reduced pressure.
The triolefin resin was isolated. The weight of this component is Wg
And The filtrate was poured into 150 ml of methanol and unreacted.
Precipitated polyester, filtered, washed and dried under reduced pressure
The unreacted polyester was isolated. Weight of this component
Is defined as Wa. The supernatant liquid after centrifugation was methanol.
Pour into 150ml to precipitate unreacted olefin resin
After filtration and washing, vacuum drying
Resin was isolated. Let the weight of this component be Wb. Less than
Each component isolated by the above method is separated by infrared spectroscopy.
As a result of analysis, it was confirmed that each was a single component. single
From the weight of each separated component, use the following formula to
Raft olefin resin content (Cg (wt%)
). [0042] (Equation 1) Reference Example 1: 2-hydroxyethyl methacryl
Rate-styrene-modified olefin resin (modified PP-
Production of 1) 230 ° C., MFR under 2.16 kg load is 1 g / 10 min,
Propylene homopolymer powder having a melting point of about 164 ° C., 2-
Hydroxyethyl methacrylate (hereinafter “HEMA”)
Abbreviation) 3 parts by weight, 10 parts by weight of styrene, t-butyl par
Add 1 part by weight of oxybenzoate, and add
After mixing, the twin-screw extruder (manufactured by Nippon Steel Works,
(Tex-30 type), cylinder temperature 180
° C, screw rotation speed 250rpm, discharge rate 5kg / h
Kneading under reduced pressure under the conditions of
Acrylate-styrene-modified olefin resin (modified PP
-1) Pellets were obtained. Structural unit based on HEMA
(IR absorption 1724cm^-1) Based on styrene
Constituent unit (IR absorption 700cm^-1) And JIS
  230 ° C of the pellet measured according to K 7210
Are shown in Table 1. Reference Example 2: 2-hydroxyethyl methacrylate
Rate-styrene-modified olefin resin (modified PP-
2) Manufacturing In Reference Example 1, the amount of HEMA added was 3 parts by weight to 5 parts by weight.
10 parts by weight to 5 parts by weight of styrene
Was carried out in the same manner as in Reference Example 1 except that
Roxyethyl methacrylate-styrene modified olefin
A system resin (modified PP-2) was obtained. Configuration based on HEMA
Content of units, content of structural units based on styrene, and M
The FR is shown in Table 1. Reference Example 3: 2-hydroxyethyl methacrylate
Production of rate-modified olefin resin (modified PP-3) 50 g of the propylene homopolymer powder used in Reference Example 1 was used.
Dissolve in 1 liter of chlorobenzene at 110 ° C. and add HEMA1
After adding 5 g, 4 g of benzoyl peroxide was added to 50 g.
Take the solution dissolved in chlorobenzene for about 1 hour
And react for 3 hours after the addition. 5 l of meta after reaction
The polymer was precipitated by pouring the reaction solution into
Separately, it was dried under reduced pressure at 110 ° C. for 6 hours to give 2-H.
Droxyethyl methacrylate-modified olefin resin
(Modified PP-3) was obtained. HEMA-based structural units
The content and MFR are shown in Table 1. [0046] [Table 1] Reference Examples 4 to 8: Polyester-modified olefin
Of resin (PEs-PP-1 to 5) Modified PP-1 to 3 obtained in Reference Examples 1 to 3, polybutylene
Interterephthalate (Mitsubishi Chemical Corporation, trade name: Novad)
Pale 5010, abbreviated as “PBT 5010” in the table),
Polyethylene terephthalate (Kanebo Co., Ltd., trade name:
PBK-1, abbreviated as “PET PBK-1” in the table)
Dry blend with the composition described in 2 above,
(Manufactured by Toyo Seiki Seisakusho), 250 ° C, 180 rpm
After kneading for 5 minutes under the conditions of
Ter-modified olefin resin (PEs-PP-1 to 5)
Obtained. Polyester in each polyester-modified olefin resin
Stergraft olefin resin (hereinafter, PEs-g-
Table 2 shows the content Cg of the abbreviated PP). [0048] [Table 2] Examples 1-4, 6-8 and Comparative Examples 1-4 Polycarbonate [Mitsubishi Gas Chemical Co., Ltd., trade name: Yu
-Pyrone S-2000, MFR is 12 g / 10 min (28
0 ° C, 2.16 kg load) and “PC S-200” in the table.
0 "), propylene homopolymer [Mitsubishi Chemical
Product name: Mitsubishi Polypro MA8, MFR is 0.
8g / 10min (230 ° C, 2.16kg load), in the table
Abbreviated as “PP MA8”] and polyester-modified OLEF
Ingredients shown in Table 3 were mixed with various resins (PEs-PP-1 to 5).
At 250 ° C. and 18 ° C. using a Labo Plastomill.
After kneading at 0 rpm for 5 minutes, pulverize and remove
A carbonate-based resin composition was obtained. Embodiment 5 Twin screw extruder (Nippon Steel Works, TEX-30)
At a cylinder temperature of 250 ° C and a screw rotation speed of 250r
pm and modified PP-2 and PBT used in Reference Examples.
5010 from the first hopper, and kneaded.
PC S-20 from the second hopper provided downstream from the par
00 and PP MA8 were charged and kneaded to obtain Table 3
Pellets of the polycarbonate-based resin composition of the formulation described
I got The kneaded product of modified PP-2 and PBT 5010
PCS-2000, before the addition of PP MA8
And analyzed, the result showed that the content Cg of PEs-g-PP was Cg.
Was 13.5 wt%. The characteristics of the obtained resin composition were determined by using an injection molding machine.
(Custom Scientific (Custom S
SC183MMX minima
The test piece injection-molded at 260 ° C.
The measurement and evaluation were performed by the following methods. The results are shown in Table 3.
You. When kneading, polycarbonate, polybutylene
Terephthalate and polyethylene terephthalate
During molding, the polycarbonate resin composition is
Immediately before drying at 100 ° C. for 5 hours. (1) Impact strength: length 31.5 mm, width
A 6.2 mm thick, 3.2 mm thick test piece was injection molded.
Izod Impact Tester (Custom Scientific
2) using Minimax CS-138TI
The notch tip R at 3 ° C. is 0.25 mm and the depth is 1.
Izod impact strength with a 2 mm notch was measured. (2) Appearance of molded article: layer of test specimen molded in (1) above
Peeling and appearance were evaluated. Something that is practically acceptable
、, defective samples are indicated by ×. [0053] [Table 3] [0054] The polycarbonate resin composition of the present invention
Is a molded product with excellent mechanical properties such as impact strength and appearance.
give.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-6-287309 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08L 23/26 C08L 67/00-67 / 02 C08L 69/00

Claims (1)

(57) [Claim 1] Component (A) having a weight average molecular weight of 10,000
Component (C) hydroxyl group-containing α, β-unsaturated carboxylic acid is added to 100 parts by weight of a resin composition comprising 10 to 99% by weight of a polycarbonate of 0 to 150,000 and 90 to 1% by weight of an olefin resin (B). The polyester-modified olefin-based resin obtained by subjecting the modified olefin-based resin to which the acid ester has been grafted and the thermoplastic polyester to the reaction step comprises 1 to 100 parts by weight of each component, and the modified olefin-based resin is Hydroxyl-containing α, β-unsaturated carboxylic acid ester 0.0 in 100 parts by weight of olefin resin
1 to 20 parts by weight and an aromatic vinyl monomer 0.01 to 5
A polycarbonate resin composition which is a modified olefin resin obtained by subjecting 0 parts by weight to a graft polymerization step.